High energy fuels and methods



United States Patent 3,221,071 HIGH ENERGY FUELS AND METHODS Eldon E. Stahly, Birmingham, Mi'cln, assignor, by mesne assignments, to Sinclair'Resear'ch, Inc., a corporation of Delaware No Drawing. Filed Dec. 28, 1959, Ser. No. 862,018 Claims. (Cl. 260666) This invention relates to mixturesof position isomers of bridged saturated polycyclic hydrocarbons having various uses, but particularly as a high energy fuel for jet, turbojet, rocket, missile and other reaction engines; to processes for forming such hydrocarbon mixtures; to intermediate mixtures useful in said processes; and to operation of jet engines by combustion of said hydrocarbon mixtures therein.

Other secondary uses for my mix'ture of compounds include heat transfer fluids, hydraulic fluids and transformer oils. lubricants, plasticizers, extenders and softeners of elastic and plastic materials.

Hydrocarbon mixtures of my compounds can have from 11 to 42 carbon atoms, such compounds having from 11 to 30 carbon atoms beingusefully liquid over wide temperature ranges. They have relatively high boiling points and relatively low depressed freezing points. More particularly, hydrocarbon mixtures hereof have a high energy content, that is, a high B.t.u. value per gallon and relatively high energy density or specific gravity. This combination of characteristics makes the present hydrocarbon mixture including position isomers outstanding for use as jet fuels.

In my prior copending applications. N. 833,996, filed August 17, 1959, now PatentNo. 3,105,351, of which the present is a continuation-in-part, I'described and claimed alkyl dicyclohexylalkane compounds preferably in the C to C range, having the above named uses, particularly as jet fuels because of their fluidity, high gravity and high B.t.u. values. Such compounds were formed by alkylatiori of two aromatic rings with a common bifunctional alkylating agent such as acetylenes, aldehydes, alkadienes, dialcohols, dihalides and the like, and hydrogenation of the alkylate product. In copending application S. N. 862,017, filed December 28, 1959, I described and claimed dicyclic jet fuels prepared by catalytic alkylation of arcmatic monocyclic hydrocarbons with vinylaromatic compounds followed by hydrogenation, wherein the fluidity, gravity and B.t.u. values of the" product is. enhanced by the presence of hydrogenated dimers of the vinyl-aromatic hydrocarbons, the dimers forming concurrently with the alkylation reaction; the amount of dimers therein can be controlled by the methods and conditions of alkylation, and the boiling range of the C to C hydrogenated fraction can be narrower than the mixture of isomers of S. N. 833,996.

I have now found that C and C cycloalkenes can be employed to alkylate aromatic hydrocarbons to produce di and tricyclic compounds wherein the cycloalkane ring is directly linked to the aromatic ring so that the finally hydrogenated product has a still higher degree of stability than the fuels disclosed in aforesaid copending applications.

The large numbers of individual components and isomers in any new product contribute to lower freezing point and higher fluidity of my new products.

They are also useful as new high stability 3,221,071 Patented Nov. 39, I965 ice The preferred alkylating components for the present invention are readily and economically available directly from cracked petroleum fractions, elg., cyclopentene and cyclopentadiene, and indene or by thermal dimerization of readily available conjugated dienes. Also such dimers are formed as by-products of other reactions of said dienes, and always accompany storage of such dienes, e.g., butadiene, piperylene, isoprene, dime thylbutadiene, and cyclopentadiene readily form cyclic dimers in amounts directly relatable to storage time and temperatures, and the dimers contain at least one ringolefinic bond; dicyclopentadiene has two ring olefinic bonds. In additionmost of the cyclic dimers: other than dicyclopnt-adiene" have alkenyl groups which were also found to alkylate aromatic hydrocarbons as disclosed in my aforesaid S. N. 862,017, filed December 28, 1959.

My compositions in the several use's mentioned above thus are mixtures of hydrocarbon compounds comprising diand tri-cyclic compounds including di and tricyclohexyl, monoand di-(lower alkylcyclohexyl) cyclohexanes and other monoand di-(lower alkyl-cyclohexyl) cycloalkanes, such as (lower alkyl-cyclohexyl)-cyclohexyl cyclopentanes, di-(cyclohexylalkyl)-cyclopentanes,- cyclohexyl perhydropolycyclopentadiene, said" hydrocarbon compounds having 14 to 30 carbon atoms when they are liquid, and being formed by (a) alkylation of an aromatic hydrocarbon with a polyolefin at least one'of the olefinic bonds thereof being of the cycloalkylene' type such' as'in alkenyl cyclohexene or alkyl substituted alkenylcyclohexene followed by hydrogenation and' (b) simultaneous dimerization of the said diolefin followed byhydrogenation. The precursor compounds for hydrogenation to produce the fuels of the present invention are formed by reaction of hydrocarbons which conform to the following Formulae I and II. Formula I components are the alkylating reactants for the Formula II components.

FORMULAI (R) Cyc (0:013

wherein R, R, R" may be the same or different members of the group consisting of hydrogen, straight or branched chain alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl or aralkyl and the total number of carbon atoms of R plus R together with the ethyl group is from 2 to 12 and of R" is 1 to 12, Cyc is a member of the group consisting of C to C monocycloalkene, cycloalkadiene and dimers, trimers and tetramers thereof, andC to C bicyclic and tricyclic alkenes and alkadienes and dimers thereof; m is an integer of 1 to 4 and n is either 1 or 2 and the total number of carbon atoms of aFbrmula I compound is in the range of 7 to 24.

Examples of alkyl are the lower straight or branched chain :alkyls having from 1 to 12 carbon atoms, 1 to 6 being preferred, i.e., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-buty1, amyl, s-amyl,'-isoamyl, t-amyl, any of the hexyls and the like up to decyl (for R or R) and up to dodecyl (for R"). Where R, R or R" in Formula I are cycloalkyll mean cyclopentyl, and cyclohexyl; and by alkylcycloalkyl I mean C to C alkyl cyclophenyl, C

to C alkyl cyclohexyl, polyalkylcyclopentyl and polyalkylcyclohexyl where the polyalkyl groups of a cyclopentyl' Examples of the Cyc group as defined for Formula I components include both mono-olefinic and di-olefinic C to C cyclic compounds and C to C mono-olefinic and diolefinic polycyclic compounds, e.g., the following groups: cyclopentene, cyclopentadiene and methylcyclopentadiene, the dimers, trimers and tetramers of cyclopentadiene and methylcyclopentadiene (as shown later the dicyclopentadiene is a tricyclic diolefin, the tricyclopentadiene is a pentacyclodiolefin and the tetramer is a heptacyclodiolefin); cyclohexene and bi-cyclohexene, bicycloheptadiene (a bicycloendoxncthylenic-dienic compound), indene; and cycloalkene-alkyl and cycloalkadienealkyl wherein the cyclic group is attached to via an alkylene group substituent, hence the cycloalkenealkyl can be e.g., cyclopentene-ethyl, C to C alkylcyclopentenealkyl, cyclohexene-propyl, C to C alkylcyclohexene-propyl, and the like.

To demonstrate the numerous isomers which can arise from positional variations in Cyc, isopropylcyclohexene group has five isomers depending on the points of attachment of isopropyl (i.e. the R" radical) in relation to the olefinic group. Variation in the aromatic reactant hence can be multiplied by five to calculate the number of positional isomers available from the process of the present invention.

Specific examples of reactants according to Formula I are cyclopentene, cyclopentadiene, cyclohexene, bicycloheptadiene, indene, the cyclic dimers of butadiene, iso prene, piperylene, dimethylbutadiene, and cyclopentadiene, the dicyclic trirners of butadiene, isoprene, piperylene, dimethylbutadiene and cyclopentadiene and the dicyclic tetramers of butadiene, isoprene, piperlyene, dimethylbutadiene and cyclopentadiene, said tetramers also being dimers of the aforesaid dimers.

By bicycloheptadiene is meant the reaction product of acetylene and cyclopentadiene.

Some specific structures of the butadiene cyclic dimer and trimers are:

Dlmer (cyclooctadlene) Dimer (vinylcyclohexene) Trtmer Trimer CH: OH UCH=CIL CH=CH3 CHz By reaction with isoprene each of the above dimers produces two trimethyl-bicyclohexenes represented by Formula I. The specific structures of four cyclic dimers of piperylene are:

Each of these by reaction with piperylene monomer produces two trimethyl bi-cyclohexenes similar to the butadiene trimers above and represented by Formula I. cyclopentadiene gives endomethylenic type polymers. Several of the polymers of cyclopentadiene are as follows:

Dimer (tricyclo) Trimer (pentacyclo) Trimer (pentacyclo) /(L \CH: Hz 0112' I/ I l/ l Tetramer (heptacyclo) Several illustrative structures of tetramers of butadiene exemplify the types of tetramers of the acyclic diolefins represented by Formula I.

-b=on on I) U CH =CH CH=CH CH CH3- C=OHg on, J

Dimer (2) CH H O 11 C 'OHa H3C- CH3 Trlmer CH3 H30 n30 "-013! H3O -on,

Tetramer (4) /CH CH CH3 3 CH3 I CH3 CCH=C CH3 but 3m Tetramer Indene of course is represented by:

Formula I The compounds of Formula I of this invention thus have in common at least one cycloalkene group containing one or two ring olefinic bonds each of which can react with alkylatable aromatic hydrocarbons of Formula II and they may or may not contain one or more side chain olefinic bonds of the alkene type (dependent on whether 11 is 1 or 2) which react with aromatic hydrocarbons of Formula II in accordance with my copending S.N. 862,017, filed December 28, 1959.

Formula II (Rlll)p l where R is hydrogen, or straight or branched chain alkyl, p is an integer from 1 to 5 and the total carbon atoms are in the range of 6 to 18.

Examples of Formula II reactants are benzene, toluene, ethylbenzene, cumene, n-propylbenzene, the butylbenzenes, the amylbenzenes, the hexylbenzenes, the heptylbenzenes, octylbenzenes, nonylbenzencs, decylbenzenes, undecylbenzenes, dodecylbenzenes, o-, m-, and p-xylenes, 0-, mand p-ethyltoluenes, o-, m-, and p-isopropyl and propyltoluenes, o-, mand p,n-propyltoluenes, the butyltoluenes, the amyltoluenes, hexyltoluenes, and the like up through undecyltoluenes, trimethylbenzene, the ethyl- Xylenes, isopropylxylenes, the butylxylenes, the amylxylenes, the hexylxylenes and the like up through the decylxylenes, the diethyl methylbenzene, the isopropylethyl toluenes, the isobutyl ethyltoluenes, the n-propylethyl toluenes, the butyl ethyltoluenes, the amylethyltoluenes, the hexylethyltoluenes, and the like up through nonylethyltoluenes, the triethylbenzenes, the propyldiethylben- Zenes, the butyldiethylbenzenes, the amyldiethylbeuzenes, and the like up through octyldiethylbenzenes, the dipropyltoluenes, the propylbutyltoluenes, the propylamyltoluenes, propylhexyltoluenes, propylheptyltoluenes, propyloctyltoluenes, dipropylethylbenzenes, ethylpropylbutylbenzenes, and the like up through ethylpropylheptylbenzenes, the tripropylbenzenes, the dipropylbutylbenzenes, the dipropylamylbenzenes, the dipropylhexylbenzenes, the propyldibutyloenzenes, the propylbutylamylbenzenes, the tributylbenzenes, the dihexylbenzenes, the tetramethylbenzenes, tetraethylbenzenes and the tetrapropylbenzenes, the octylbutylbenzenes and the like.

By reaction of compounds of Formula I with those of Formula II in the presence of at least one Friedel-Crafts or Lewis acid catalyst or such catalysts with promoters, alkylated products having at least two cyclic groups represented by Formula III are formed:

Formula III wherein R, R, R", R, Cyc, m, n, and p have the same significance as in Formulae I and II and 1 to 3. Thus, when n is 1, q is at least 2; and when q is 1, n is 2.

A limitation of the above formulae is applied when used as a liquid fuel is intended, namely that the carbon count of the components within the scope of the formulae be within 14 to 30.

Thus the alkylation of Formula I compounds by Formula II aromatic compounds produces a mixture of precursor products wherein in addition to alkylation of Formula 11 compounds by the ethylenic side chain, the Formula II aromatic compounds are also alkylated by the olefin group in the -Cyc-nucleus, and each alkylation group entering the alkylation results in an increased numbers of isomers resulting from the R substituent groups Also this precursor mixture contains dimers of the Formula I compounds which enhance further the number of components in the precursor product, and also in the final hydrogenated product.

The process of producing the high-gravity high energy fuels of my invention in its simplest definition is the alkylation of the aryl ring of an arylhydrocarbon of Formula II by reaction therewith of a cycloolefin, including cyclodiolefin, or cyclopolyolefin of Formula I having at least one ring unsaturated olefinic bond (as in cyclopentene or cyclohexene ring), in the presence of a catalyst selected from the class of Friedel-Crafts catalysts and Lewis acids, followed by hydrogenation, to produce C to C liquid fuels. Higher than C to C alkylation products may be formed simultaneously in lesser amounts and where a fuel of improved viscosity is desired the higher boiling products can be readily separated therefrom as residue from distillation under reduced pressures.

The specific gravity of such liquid mixtures will generally exceed about 0.85 and by the term high gravity as used herein, I mean a liquid having this minimum or higher gravity. The B.t.u. value will usually exceed about 135,000 B.t.u. per gallon and by the term high energy as used herein I means a combustible mixture having the minimum or higher B.t.u. value. For instance, the gravity of the jet fuels hereof usually lie in the range of about 0.85 up to about 0.91, and the B.t.u. value preferably ranges from about 135,000 up to about 145,000 B.t.u. per gallon.

In the above precursor Formula III, the Cyc-group may be mono and polycycloalkene, e.g., alkylcyclohexene ring, or mono and polycycloalkenealkyl radicals, and mono and polycycloakladienealkyl and like radicals derived from the cyclo-olefin components Formula I. The hydrogenation of Formula III compounds to form the products of the present invention saturates first any unreacted olefinic unsaturation under relatively mild conditions e.g. at less than 100 C. under 100 to 250 psi. hytions (higher temperatures and higher hydrogen pressures drogen pressure, then finally the aromatic rings are hydrogenated under more stringent hydrogenation conditions (higher temperatures and higher hydrogen pressures).

Thus my invention discloses a new composition of matter comprising a mixture of fully saturated polycyclic alkane position and geometric isomers having Formula Formula IV yc L wherein R, R and R are members of a group consisting of hydrogen, straight and branched chain alkyl, alkylcycloalkyl, cycloalkyl, cycloalkylalkyl; R is a member selected from the group consisting of hydrogen, straight and branched chain alkyl; R plus R together with the ethyl radical has from 2 to 12 carbon atoms and R has from 1 to 12 carbon atoms; R is a member selected from the group consisting of hydrogen, straight and branched chain alkyl and said radical having 1 to 12 carbon atoms; Hyd. Cyc is a hydrogen saturated radical of C to C monocyclic cycloalkene, cycloalkadiene and dimers, trimers and tetramers thereof and a hydrogen saturated radical of C to C bicyclic and tricyclic alkenes and dimers thereof, as defined above; for example, cyclopentane, cyclohexane, bicyclohexane, endo-methylene cyclohexane, condensed polycyclopentane-endo-methylene-cyclohexane rings (derived from di-, tri-, and tetracyclopentadiene), perhydroindan, and cyclopentadienealkyl groups; said isomers being formed predominantly by alkylating a compound of the Formula II:

with a cycloalkene compound of Formula I:

in the presence of a catalyst selected from the group of Friedel-Crafts and Lewis acid catalysts and said catalysts with a promoter, in which formulae R, R and R are selected from the group consisting of hydrogen, straight and branched chain alkyl, cycloalkyl, alkylcycloalkyl, aralkyl and cycloalkylalkyl; R plus R together with the ethylene radical has from 2 to 12 carbon atoms and R has from 1 to 12 carbon atoms; R is a member selected from the group consisting of hydrogen, straight and branched alkyls and said radicals having 1 to 12 carbon atoms, Cyc is a radical of C- to C monocyclic cycloalkene, cycloalkadiene and dimers, trimers and tetramers thereof and 7 to 12 carbon atoms bicyclic and tricyclic alkenes and dimers thereof; m is an integer from 1 to 4, n is an integer from 1 to 2, p is an integer from 1 to 5, q is an integer from 1 to 3 when n is 1, q being at least 2 and when q is 1, n being 2; and the total number of carbons is in the range of 11 to 42 and hydrogenating the reaction product.

The alkylation is preferred to be conducted in the pres ence of Lewis acids or Friedel-Crafts catalysts. By Lewis acids are meant substances having ability to accept electrons (more conventional definition of acids is substances having a tendency to lose a proton). Thus Lewis acids include any substance in non-aqueous systems as well as in aqueous systems, which readily accepts a pair of electrons and thus includes Friedel-Crafts catalysts conforming to HMeX where Me is a metal of n-1 valence, X=halogen and n=an integer from 2 to 6, the (MeX ion being readily formed therefrom e.g., BF4 AlCl SnCl SbCl and the like. Lewis acids also include HF, H2804, P2O5H2SO4, H3PO4, H4P2O7, and the like which may be used in both aqueous and anhydrous catalyst systems of this invention.

The procedure found best adapted for reacting components of Formula I with components of Formula II to produce alkylation products of Formula HI is briefly as follows:

The catalyst and Formula II components are placed in a reaction vessel. The component of Formula I are diluted with the components of Formula II in a ratio of one mole of Formula I component to about 2 moles of Formula II component and this mixture is then added gradually to the reaction vessel while stirring and cooling to maintain the desired temperature usually selected from the range of '70 to +50 C. The amount of component I added is regulated so that in the final reaction mixture the ratio of Formula II to Formula I components is from 5/I1 to 10/ 1. This provision for dilution of Formula I component promotes the alkylation reaction and minimizes the polymerization of Formula I component. Additional reaction time of from 1 to 2 hours after completion of the reaction is provided to complete the alkylation reaction; the reaction vessel contents after standing for an hour at room temperature separate into two layers, the upper hydrocarbon layer is separated, washed with an equal volume of water, a half-volume of 5% sodium hydroxide or sodium carbonate solution, and finally with an equal volume of water. The wet hydrocarbon layer may be dried with silica gel, alumina, calcium sulfate or other drying agent, or it may be distilled directly, the water being removed from the products along with the first hydrocarbon distillate therefrom, the first distillate being unreacted reactants of Formula I and II. Continued distillation after removal of the unreacted reactants yields the liquid products of the alkylation as distillate, the solid high boiling products remaining as bottoms which do not distill without decomposition above 200 C. at 2 mm. pressure.

The total liquid distillable product is fully hydrogenated over Raney nickel or Raney cobalt catalyst at 100 to 200 C. or even higher temperatures in a suitable solvent such as n-pentane, n-heXane, n-heptane, cyclohexane, methyl cyclohexane or the like, under non-critical hydrogen pressures of 100 to 5000 p.s.i. hydrogen pressure. If only partial hydrogenation is desired the temperatures, pressures, and catalyst concentration become somewhat critical; temperatures up to 100 C. and pressures up to 1000 p.s.i. are sufficient to saturate olefinic unsaturation both acyclic and alicyclic, higher temperatures and pressures being required to completely hydrogenate the aromatic rings.

Illustrative examples are given to demonstrate the types of reactants which are useful in the present invention. In the following examples percentage values are percent by weight unless otherwise stated.

EXAMPLE 1 Alkylation of toluene with vinylcyclhexene-3 Seven and one half moles (690 grams) of toluene (boiling range 2129-232 F.) was charged to a react-ion vessel equipped with a mechanical stirrer, dropping funnel and thermometer. To the reaction vessel was also added 110 grains of 96.9% sulfuric acid and 18.75 g. of boron fluoride-phenol complex (General Chemical Division of Allied Chemical Co.) containing 26% boron fluoride, the acid-boron fluoride complex serving as alkylation catalyst. The toluene-catalyst mixture was cooled by placing the reaction vessel in an ice bath, and when the temperature was 8 C. one mole of Eastman Kodaks vinylcyclohexene-3 (1108 g.) was added dropwise at a rate sufficient to maintain a reaction temperature of 612 C. The addition time of the vinyl cyclohexene was 1.2 hours; stirring was continued for an hour while maintaining 5 C. temperature. The acid layer was separated and the upper layer (A) was washed with two portions each of 100 ml. (96.9%) sulfuric acid to remove any hydrocarbon sulfate present from the side reaction of the vinylcyclohexene-B with sulfuric acid, and then with 200 ml. of 20% sodium carbonate solution. All three acid layers were combined, diluted with 1500 g. of a mixture of ice and water, and extracted with 450 ml. toluene. The toluene plus extract (B) was washed with 530 ml. of sodium carbonate solution, filtered through a bed of sodium chloride, and a few ml. of emulsion breaker (a combination of Aerosol OT and Aerosol 22, both of American Cyanamid Corp.) were added. The upper layer B was combined with layer A above and distilled. The first toluene distillate carried out the traces of water by azeotropic distillation. After removal of Hydrogenation of fraction 1 was conducted over Raney nickel catalyst (10 .g.) in pentane at 1500 p.s.i. hydrogen while increasing the temperature from 100 to 200 C.

over a 5 hour period. Evaporation of the pentane left a quantitative yield of hydrogenated product having a gross energy of combustion of 19,620 B.t.u./lb., a net energy of combustion of 18,385 BaLlL/lb. and 139,540 Btu/gallon, d 0.910, n 1.4912, and B.P. 275 to 335 C. at 745 mm.

EXAMPLE 2 Alkylation of toluene with butadiene dimer The procedure of Example 1 was used to react 7.5 moles of toluene (690 g.) with one mole of butadiene dimer (vinylcyclohexene-3) prepared by thermal dimerization of butadiene at 250 C. in toluene solution, and separation therefrom, BJP. 126*128 C./745 mm., 11 1.4250. As catalyst 25 g. of boron fluoride-phenolate (26% boron fluoride) was used (from Allied Chemical Co.) but without sulfuric acid. The toluene-catalyst mixture was cooled to 5 C. and the dimer was added dropwise at a rate to maintain 5:2 C. over a period of 2.05 hours. Stirring was continued for 1.5 hours at 5 C.; 200 ml. hot 20% sodium hydroxide was added and the mixture warmed to C. The emulsion was broken with sodium chloride (5 g.) and isopropanol (5 ml.). The upper layer was washed by boiling with 300 ml. Water for 30 minutes. An inter-mediate emulsion was broken with a few ml. acetic acid and 10 g. sodium chloride. The upper layer was distilled to obtain toluenefree product.

No. Grams B.P., C./rnm. Hg M20 1 5s 117-205 2-5 1.5392. 2 84 Solid Resin.

Hydrogenation as in Example 1 gave a fuel of 19,640 B.t.u./lb. gross energy of combustion, and a net energy of combustion of 139,690 Bin/gallon.

EXAMPLE 3 Alkylazion of toluene with piperylene dimer Toluene (boiling point 229232 F.) was reacted with piperylene dimer prepared by thermal dimerization of piperylene (from Burke Research Co.) and having a boiling point of 111 to 114 C. at 145 mm. pressure, an n 1.4715. The four isomeric cyclic dimers described herein before were indicated to be present by spectroscopic analysis of the piperylene dimer.

The procedure of Example 1 was employed 736 g. of toluene (8 moles) and 205 g. (2 moles) of 95.5% H 80 catalyst being charged to the reaction vessel at the start. After cooling this mixture of toluene and acid one mole (136 g.) of the piperylene dimer diluted with two moles (184 g.) toluene was added dropwise at a rate sufiicient to maintain a reaction temperature of 3i1 C. The time of addition was 2.75 hours. Stirring at 2:1 C. was continued for 1.8 hours. The acid layer was separated and diluted with an equal volume of water; the new upper layer from this diluted acid was combined with the first hydrocarbon layer, and the combined hydrocarbon layer was washed with 300 ml. of 3% salt water, and twice with 500 ml. of 5% sodium carbonate solution. Partial emulsion was broken with 5 ml. carbon tetrachloride, and filtration of the upper layer through sodium chloride.

Distillation removed the toluene and moisture, leaving 156 grams of product which gave the following fractions upon distillation at reduced pressure.

The total yield was based on the cycloolefin (piperylene dimer) feed.

Hydrogenation of (1) above was carried out at 1400 p.s.i. hydrogen in pentane with 25 g. Raney nickel catalyst at 180 to 225 C. A substantially quantitative yield of hydrogenated product resulted having n 1.4935, d 0.908, a gross heat of combustion of 19,495 B.t.u./lb. (18,245 B.t.u./lb. net, and 138,020 net B.t.u./gallon).

EXAMPLE 4 Alkylation of toluene with isoprene dimer Example 3 was repeated replacing the piperylene dimers with isoprene cyclic dimers (supplied by Burke Research Co., Detroit, Michigan), boiling at 158 to 178 C./750 mm. Hg, sp. g. 0.84 and containing the four isomers hereinbefore disclosed.

Eight moles of toluene (736 g.) and two moles 95.5% H SO (205 g.) were precooled to 4 C., and 205 g. isoprene dimer (1.5 moles) were diluted with 2.5 moles toluene and added dropwise at a rate which maintained a reaction temperature of 311 C. The time of addition was 3.5 hours and additional stirring time at 3 C. Was 1.75 hours.

The acid layer was separated from the hydrocarbon layer (A) diluted with 100 ml. water, and the resultant upper layer (B) was added to the first layer (A). The total hydrocarbon layer was washed with 500 ml. water. The upper layer was separated and washed with 250 ml. sodium carbonate (5%) solution and then with 500 ml. water. It was then distilled to remove toluene, C dimer, and moisture therefrom. The remainder (235 g.) represented 115% yield. It was distilled to give 85% distilling at 125 to 197 C./2 mm. Hg (n 1.5220) and 15% brown residual resin.

Hydrogenation of the distillate was conducted as in Example 3 using 20 g. Raney nickel and 500 ml. pentane per 100 g. distillate. The hydrogenated product, obtained in substantially quantitative yield showed a boiling point of 302322 C./745 mm. Hg, n 1.4879, (1 0.897, a net heat of combustion of 18,275 B.t.u./lb. and 135,970/B.t.u. per gallon.

EXAMPLE 5 Reaction of xylenes with dipentene Dipentene (Hercules Co., #122) and Sinclairs 5 xylene (containing 21% ethyl benzene, 2% toluene, 19% o-xylene, p-xylene and 48% m-xylene) were used in this example with sulfuric acid catalyst, using the procedure of Example 1. The xylene (1700 g.) was stirred with 203 g. of 96.6% sulfuric acid and cooled to 5 C. Dipentene (545 g.) was added dropwise over a period of 3.25 hours while stirring and maintaining a temperature of 5:1 C. Stirring was continued an additional 150 minutes, the reaction mixture was allowed to settle, the acid layer separated and the upper layer was washed with water (1 liter), 5% sodium carbonate solution (1 liter), filtered through a salt bed, and distilled to remove the traces of moisture, toluene and unreacted dipentene. The product gave 72% distillate at 125 to 174 C./rnm. (n 1.5197) and 28% brown solid resin.

Hydrogenation of the distillate as in ExampTeTEave substantially quantitative yield of fuel boiling at 316 to 340 C./745 mm. Hg, 11 1.4915, r1 0.894, and a net heat of combustion of 135,850 B.t.u./ gallon.

EXAMPLE 6 Reaction of xylenes with dipentene Example 5 was repeated using 100 g. of boron fluoride phenolate catalyst (26% BF instead of the 203 g. of sulfuric acid, and using an additional time for the dipentene of 5 hours. By use of this catalyst a 130% yield of product based on dipentene was obtained, 60% of which distilled at 167 to 225 C./mm. When hydrogenated as in Example 5, the fuel showed a net heat of combustion value over 136,000 B.t.u./gallon.

12 EXAMPLE 7 Reaction of toluene with dicyclopentadiene Using the procedure of Example 1, one mole (132 g.) of dicyclopentadiene was added to toluene (8 moles, 737 g.)-boron fluoride phenolate (25 g. containing 26% boron fluoride) at 5:1 C. over a period of 1.5 hours. Stirring was continued for an hour thereafter at 165 C. The reaction mixture was diluted with a liter of pentane and the mixture was worked up as in Example 5. After distillation to remove the unreacted toluene and dicyclopentadiene, a yield of 162 grams was obtained, 42% of which distilled over at 149 to 215 C. at 1 mm. Hg pressure (n 1.5525). Hydrogenation as in Example 1 gave substantially a quantitative yield of product boiling at 302-323 C./745 mm., n 1.5009, (1 0.939, and a net heat of combustion of over 142,000 B.t.u./ gallon.

EXAMPLE 8 Reaction of benzene with dicyclopentadiene Example 7 was repeated but substituting 18 moles of of benzene for the 8 moles of toluene and 4 moles of dicyclopentadiene for 1 mole of dicyclopentadiene, and g. boron fluoride-phenolate for the 25 g. used in Example 7. 250 g. of product resulted distilling from to 180 C./rnm. (11 1534).

Hydrogenation as in Example 7 resulted in a fuel having a heating value over 142,000 B.t.u./ gallon.

EXAMPLE 9 Reaction of toluene and vinylcyclohexene-3 Example 1 was repeated employing a 2/1 ratio of toluene to vinylcyclohexene-3. The product was recovered similarly and the distillate (70% yield on vinylcyclohexene) was hydrogenated as in Example 1. The product, recovered practically quantitatively, distilled at 275 to 330 C./745 mm. and had a net B.t.u. value over 135,000 B.t.u./gal. The alkylation product contained in preponderance dimer of vinylcyclohexene which contributed to the fluidity and energy value of the hydrogenated fuel.

EXAMPLE 10 Reaction of ethylbenzene with piperylene dimer Example 3 was repeated but substituting 10 moles of ethylbenzene for the toluene of that example (8 moles in the reactor with the acid and 2 moles as diluent for the dimer). The final hydrogenated distillable product (over 100 wt. percent on the piperylene dimer feed) showed an energy of combustion over 135,000 net B.t.u./ gallon.

Many isomers of the alkylated product are available result-ing from the positions of attachment of the R" and groups to the Cyc moiety of Formula III product precursor to the hydrogenation which produces Formula 1V products of my invention. These many isomers are further enhanced by the several positions of attachment of R' to the aromatic nucleus in relation to the point of attachment of said aromatic nucleus to the Cyc group and a corresponding number of isomers appear in the saturated Formula IV products. The number of individual hydrocarbon components is further enhanced by the polymers, particularly the dimers, of Formula I compounds which are concurrently formed in the alkylation reaction in the presence of Friedel-Crafts and Lewis acid catalysts, sa-id dimers appearing in the hydrogenated form in my products. The hydrogenated dimers are liquids when they contain C to C carbon atoms and contribute both to the fluidity and high B.t.u./gallon of my fuels. It has been found that the greater the number of individual components, the greater is the fluidity of my fuel and the lower the freezing point thereof.

One of the advantages of my present invention is that it utilizes aromatic feed stocks e.g. a petroleum C to C aromatic fraction or reformate, which are readily available from the petroleum industry (Formula II components) together with cycloalkene derivatives (Formula I components) that are readily obtained as by-product polymers of conjugated dienes, these by-products having found very little use prior to my present invention, i.e., dimers, cod-imers, trimers and cotrimers and tetramers and cotetramers of butadiene, piperylene, isoprene, cyclopentadiene and the like.

It is preferred to have a product containing both 2 and 3 cyclic groups. Thus it is preferred to alkylate with a d-i-unsaturated compound (Formula I) in such a manner that two aromatic components (Formula II) are attached, one via each double bond, in at least a portion of the Formula I reactant, the remainder of the product being equally divided between single alkylation of each double bond. The procedures used in my present invention make this possible to effect.

To illustrate this reaction to form compounds of Formula III, the alkylation reaction products of toluene (Formula II reactant) and vinylcyclohexane-3 (Formula I reactant) with a Friedel-Crafts catalyst involves the addition of toluene, in the mand p-positions to the methyl group, to one side of an ethylenic bond, the hydrogen from the substituting position of the toluene going to the other side of the double bond, and also will contain dimers of the Formula I reactant. Thus the d-icyclic reaction products (Formula III) from toluene and vinylcyclohexene-3 will contain the following components.

I-A. Alkylation products (Formula III) 3-cyclohexenyl-l-ethyltoluene (3 isomers) 2-vinylcyclohexyl-toluene (3 isomers) 3-vinylcyclohexyl-toluene (3 isomers) I-B. Dimer products (Formula I):

3-cyclohexenyl- 1-ethyl(vinylcyclohexene-3 (2 isomers) 3-cyclohexenyl-2-ethenyl(2- and 3-vinylcyclohexane) (2 isomers) 2,4-bis-(3-cyclohexenyl)-butene-l and -2 (2 isomers) (2-vinylcyclohexenyl)-2- and 3-vinylcyclohexane (2 isomers) (3-vinylcyclohexenyl)-2- and 3-vinylcyclo'hexane (2 isomers) Further, there will be present in the reaction product the following tricyclic components.

II-A. Alkylation products (Formula III) from vinyl- I cyclohexene:

l-( l-tolylethyl)-2-cyclohexyl-toluene (9 isomers) 1( l-tolylethyl)-3-cyclohexyl-toluene (9 isomers) I=IB. Alkylation product-s (For-mula III) from preceding IB dimers:

2-( l-tolyl -cyc1ohexyll-ethyl-(vinylcyclohexene-3) (six isomers) 3-( l-tolyl -cyclohexyll-ethyl- (vinylcyclohexene-3) (six isomers) 2-(tolyl)-cyclohexyl-2-ethenyl(2- and 3-vinylcyclo- In addition to the above, many solid polycyclic compounds are'present. Obviously when the above toluenevinylcyclohexene reaction products are hydrogenated a corresponding large number of hydrogenated isomers are found to be present. In general the fuels comprise only minor amounts of most of the position and geometric isomers, the amount depending on the relative activities of the o-, mand p-hydrogens of toluene, and also on the relative activities of the vinyl and ring unsaturation of vinylcyclohexene-3 and its dimers.

It has thus been found that stable high gravity, low freezing (as low as 50 C.), high energy fuels result, from my invention, the many isomeric components of Formula IV type including hydrodimers and hydrotrimers of Formula I and II reactants contributing to the fluidity and low freezing point, of the C to C hydrogenated products of my invention. Other valuable uses as well as in fuels have been found for these products as hereinbefore described.

As stated hereinbefore Friedel-Crafts and Lewis acid catalysts with or without promoters are useful for the alkylation reactions described herein. Friedel-Crafts catalysts are often used With promoters, e.g., aluminum chloride is often used in admixture with promoters such as nitromethane, nitrobenzene, carbon tetrachloride, alkyl halide, alcohols, water, hydrogen chloride and the like.

The reaction may be run in three different ways to obtain distinctly modified products in each. It will be apparent that in the process wherein a Lewis acid catalyst of the type described herein is employed, direct addition of such catalyst to the Formula I component would result in immediate polymerization thereof. This may be controlled by my procedures so that either low amounts or large amounts of dimer may be obtained as desired. Some of the dimerized products are present in even the preferred most efficient alkylation method A. The quantity of dimer formed is readily controlled by these methods.

A. ALKYLATION METHOD According to this method, the non-polymerizable Formula II component which may be a common diluent or solvent like toluene, is first charged to the reaction vessel to serve as a diluent reactant. The catalyst may then be suspended therein. Since the immediate reaction comprising either alkylation or dimerization Will take place with a polymerizable reactant, the Formula I component is added only dropwise, so that it is immediately diluted by the Formula II diluent and reacts therewith catalytically. By this method the polymerizable component is maintained at a very low concentration in Formula II reactant diluent and the reaction is largely alkylation of the diluent. Small amounts of dimer may also be formed and such may ultimately reenter the alkylation reaction.

B. COMBINED ALKYLATION AN D DIMERIZATION According to this procedure, the polymerizable component is not particularly protected from substantial polymerizing, but rather both polymerization of the Formula I compound as well as alkylation of Formula II takes place. Thus, both types of compounds are charged together with the catalyst to the reaction vessel, so that large amounts of dimerization take place forming dimers which in turn may ultimately enter into the alkylation reaction. Of course, a large portion of the reaction is direct alkylation of Formula II by Formula I compound without dimerization.

C. CONTROLLED CATALYST ADDITION A third procedure is that of forming a mixture of Formula I and Formula II compounds in any selected of a wide range of proportions and adding the catalyst slowly and gradually to the mixture. The reaction is controlled approximately by the rate of catalyst addition. Again, both dimerization and alkylation takes place as in B.

It will be appreciated that combinations of these methods can be applied, for example, any of methods A, B and C may be modified by further addition of diluent Formula II added at intermediate stages as the reaction proceeds, to maintain the degree of alkylation if desired.

In carrying out the alkylation reaction, where predominantly the bicyclic compound is desired, the alkyl benzene is usually used in substantial excess, e.g., a 2 to 3 times molar excess in relation to the equivalent quantity of alkylating group material (vinyl equivalent of Formula I) employed and where higher polycyclic side reaction compounds (such as included in Formulae III and IV), a lower ratio down to about to 3 moles of Formula II compound per equivalent of alkylating compound (Formula I) is used. The catalyst may be added thereto at below room temperature, and if the alkylating compound is difficult to react, the temperature may be raised; if the alkylating compound is highly reactive, the temperature may be lowered, applying cooling or refrigeration as needed, and the alkylating group material is usually added slowly, such as dropwise over a several hour period usually 2 to 12 hours, with continued agitation in order to avoid excess side reaction thereof, the conditions being modified depending on the activity of the reagents, and on the desired product.

When the alkylation reaction does not terminate by joining of only two ring groups, it is preferred for high yield of fuels, to allow the reaction to convert only a portion, such as about /3 of the available alkyl benzene, to the Formula III compound before terminating the reaction. The reaction products (Formula III compounds containing minor amounts of dimer or dimer derived compounds) are then recovered from the reaction mixture and the excess unreacted compounds such as alkyl benzene are recycled to the reactor.

Formula I compounds containing two functional groups such as vinylcyclohexene or methyl isopropenylcyclohexene can result in both monoand di-alk lation, i.e., alkylation of two aromatic nuclei, in the sa he reaction in the presence of the selected acid or I iedel- Crafts catalyst.

In the instance of reacting in the presence of aluminum chloride catalyst or an equivalent Friedel-Crafts catalyst, the alkyl benzene compound (Formula II), and the alkenyl-cyclohexene reactant (Formula I) are first mixed, and the mixture usually is cooled to from 70 to 0 C., and then the aluminum chloride can be added in any suitable manner, even rapidly, with or without a promoter. The reaction mixture is maintained at below 5 C. for 1 to 5 hours and is then permitted to warm up gradually to 25 C. over a period of l to 2 hours to complete the reaction.

After the position isomeric compounds of Formula III together with the position isomers, codimers and dimers (from Formula I compounds) are prepared, they are freed of catalyst residues by decantation, filtration and/ or Water washing with or without the aid of acid for Friedel-Crafts catalysts removal, followed by an alkaline aqueous Wash; or in the case of the acid catalyst, catalyst removal is accomplished by washing with only water and/ or alkaline aqueous wash. In most instances the unreacted starting materials are removed by distillation, the distillate having traces of Water present from the washing; the distillate after drying, e.g., with silica gel, calcium sulfate, and the like is recycled back to feed tanks for the alkylation process. The product compounds remaining from said distillation are then hydrogenated. Before hydrogenation, the Formula III product may be further distilled for greater purity to separate the tricyclic and polycyclic compounds therefrom; or the tricyclic and polycyclic compounds may be hydrogenated therewith and separated, if desired, from the hydrogenated product (Formula IV). The hydrogenation is usually carried out in a diluent, e.g., a paraffin solvent such as pentane or hexane, or a cycloalkane solvent such as cyclohexane or methylcyclohexane in the presence of a hydrogenation catalyst for aromatic compounds, etc. In the examples herein an active Raney nickel or Raney cobalt catalyst was preferred using from 10 to 15 g. per mole of Formula III compound.

In order that hydrogenation of the aromatic rings of Formula III compounds proceed at a reasonable rate, hydrogen is employed at non-critical elevated pressures, usually from about 500 p.s.i. to 5,000 psi. To hydrogenate these aryl compounds, the temperature is raised non-critically above a minimum temperature, usually 100- 200 C., but sometimes higher, until hydrogenation commences. When the Formula III compounds contain unsaturation other than aromatic unsaturation such can first be removed by hydrogenation under mild conditions (below 100 C.) to yield intermediates which can have use as plasticizers, extenders, hydraulic fluids etc. and these materials can, of course, be exhaustively hydrogenated to form the polycyclic alkanes hereof. In such hydrogenation, each aryl ring usually has a minimum or threshold hydrogenation temperature which must be exceeded and this depending on the activity of the catalyst employed and on the position of the alkyl substituents in the individual aryl rings.

By control of catalyst activity, temperature, hydrogen pressure and selection of solvent, I can obtain selective hydrogenation, i.e., I can hydrogenate only a single aromatic ring of these bi-aromatic ring compounds, e.g., of Formula III, thus, producing compounds in which each alkenyl group of R, R, R" and R" of Formula III have been converted to alkyl and some, but not all, of the aromatic groups of Ar, or included in the Formula II radical of Formula III, have been hydrogenated to a cycloalkane group. Thus the Formula III product can have all side chains and one of the benzene groups of Formula III bydrogenated to a cycloalkane group, but not all, if so desired.

EXAMPLES 11 TO 20 As mentioned hereinbefore, each catalyst system produces an ultimate product differing in amounts of the various isomers of hydrogenated alkylate and hydrodimers present. Also, the composition varies with conditions of alkylation. It has been further found that for each catalyst system there are preferred conditions of operation to attain optimum yields of precursors for hydrogenation to high energy fuels. When maximum alkylation and a minimum of dimer formation (including self-alkylation) is desired the preferred conditions for producing highest yields are shown in Table I, for a number of Lewis acids and Friedel-Crafts type catalysts. The ratio of mono unsaturated (Formula I) hydrocarbon to saturated aromatic compounds (Formula II) is always below 0.5 when alkylate is the desired major product, and the ratio is below 0.25 for diunsaturated compound to saturated aromatic compound.

TABLE 1 Example No. Catalyst 11 Aluminum chloride/nitrobenzene (1/ 3 mole ratio).

12 Aluminum chloride/nitromethane (1/10 mole ratio).

13 Sulfuric acid (-98%).

14 Ferric chloride.

15 Methane sulfonic acid/boron fluoride 10/3 mole ratio).

16 Aluminum chloride.

17 L. Aluminum chloride/carbon tetrachloride (1/ 1 mole ratio).

18 Hydrogen fluoride.

19 Aluminum chloride/hydrogen chloride (1/1 mole ratio).

20 Hydrogen fluoride/boron fluoride (/1 mole ratio).

TABLE ICntinued [Preferred conditions for the alkylation of aromatic hydrocarbons (Formula II) with eycloalkene type hydro carbons (Formula I) employing Lewis acid or Friedel-Crafts catalysts to produce optimum yields of precursors for the fuels of the present invention (Formula II) compound exemplified, in Examples 1 to 10, by

benzene, toluene, xylenes, ethylbenzene, cumene,

ethyltoluene, butylbenzene, amylbenzene] Molar ratios Percent Example Total polymer and Ethenoid Nq.- Temp, 0. hours of alkylated Proceaddition, Continued Catalyst- Formula reaction dimer in dure 1 hours ethenoid II/Foralkylate group mula I 0.4/1 7 4/1 1. 5 0.3 1. 0/1 5/1 1. 5-2 30 0.3 0. 5-1. 0/1 3-5/1 1-2 1.0 1/1 3-5/1 3 0. 5 0 5-0. 6/1 3-5/1 12 1. 0 -40 to 20 0. 1/1 5/1 2-3 1. 0 -40 to 30 0.2/1 5/1 2-3 50 1.0 -60 to 30 5/1 5/1 1. 5-2 25 0.65 70 to 50 0. 2/1 5/1 2-3 35 0.5 70 to 50 5/1 5/1 1. 0-1. 5 50 0.65

{Procedure A: Ethenoid hydrocarbon added gradually to aromatic hydrocarbon catalyst mixture while agitating VlgOIOllSly and cooling the reaction flask in a cold bath (ice and salt water for 0 C. and above and Dry Ice-alcohol bath for 0 to 70 C.)

2 Ratios in this column based on mono-unsaturation of Formula I compounds.

In similar examples it was demonstrated that boron fluoride-phenolate containing one or two moles phenol per mole of boron fluoride can be used in place of the boron fiuoride-etherate, or boron fluoride-methyl amine complexes, boron fluoride-pyridine complexes and the like can be used as an alkylating catalyst under the conditions outlined in Table I examples, in the process of the present invention. Likewise aluminum chloride promoted with water, alcohol, organic acid, a phenol, ether, ester, alkyl halide, a polyhalogenated methane, an amine, ethane, or propane (the promoter being used in a molar amount of'l to 0.1 mole per mole of catalyst under the conditions exemplified in Table I) can be used.

Thus by selective use of Friedel-Crafts and Lewis acid catalysts and conditions of operation either (A) high yields of alkylated isomeric (Formula III) compounds with minor amounts of dimers can be produced as precursors for hydrogenation, the products of which in the range of G to C molecules are useful as liquid fuels, lubricants, plasticizers for plastic materials, softeners and extenders, hydraulic fluids, dielectric fluids and the like, and in the range of greater than 30 carbon atoms are useful as solid fuels, greases, plasticizers, heat materials and the like, or (B) high yields of dimers with low yields of alkylate isomers (Formula III) are obtainable as precursors for hydrogenation and after hydrogenation these products also show high fuel value, and have uses similar to those outlined for products in (A) above (e.g., Example 9).

In summarizing it is apparent that the fuels exemplified herein fall within the desired range of 130,000 to 145,000 B.t.u./ gallon of fuel. Thus by the present invention novel liquiddicyclic high energy hydrocarbon fuels, the mixtures of cycloalkyl alkylcycloalkane derivatives including hydrogenated dimers of cycloolefinic and polycyclolefinic hydrocarbons are provided wherein the total number of carbon atoms is in the range of 14 to 30. Also are provided solid dicyclic and tricyclic hydrogenated fuels containing from 30 to 42 carbon atoms which in minor amounts may be retained in the liquid fuels, or may be separated for use as solid fuels. All such saturated products have other advantageous usages such as lubricants, plasticizers, dielectric oils, hydraulic fluids, power transmission fiuids and the like.

The use of such new fuels in admixture with otherhigh energy fuels is' also visualized thus providing a means of enhancing the fuel value of presently used hydrocarbon hydrogenated dimers of cycloolefinic and polycycloolefinic fuels such as kerosene, dialkylcyclohexane, paramenthane and the like. Further they are valuable for admixing with boron hydride, the alkyl boron hydrides, the trialkyl borons, and the like, to minimize fire and toxicity hazards inherent with these boron derivatives per se.

While there have been described herein what are at present considered preferred embodiments of the invention, it will be. obvious to those skilled in the art that minor modifications and changes may be made without departing from the essence of the invention. It is therefore to be understood that the exemplary embodiments are illustrative and not restrictive to the invention, the scope of which is define-d in the appended claims, and that all modifications that come within the meaning and range of equivalency of the claims are intended to be included therein.

Defined formulas For brevity the formulas incorporated by reference in the'appended claims, and the substituent portions thereof, are here defined, as follows:

Formula I [IV-OH] R- n-l (R)rn1 yO Formula II Formula III Formula V (Ivan-i Cyc m-1 in which Formulas I to VII:

R, R and R are members of the group consisting of hydrogen and straight and branched chain alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl and aralkyl radicals, R and R together with the two adjacent carbon atoms having 2 to 12 carbon atoms and R" having to 12 carbon atoms;

R is a member of the group consisting of hydrogen and straight and branched chain alkyl radicals having 1 to 12 carbon atoms;

Cyc is a member of the group consisting of cycloalkene and cycloalkadiene radicals having 5 to carbon atoms and dimers, trimers and tetramers thereof, and dicyclic and tricyclic alkene and alkadiene radicals having 7 to 12 carbon atoms and dimers thereof;

Hyd. Cyc is a saturated radical obtained by hydrogenating a Cyc radical;

m, n, p and q are integers from 1 to 4, 1 to 2, 1 to 5, and 1 to 3, respectively, the sum of n and q being an integer greater than 2.

I claim: 1. A composition of matter comprising a mixture of position and geometric isomers of at least one of Formulas IV, V, VI and VII,

in which Formulas IV to VII:

R, R' and R are members of the group consisting of hydrogen and straight and branched chain alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl and aralkyl radicals, R and R together with the two adjacent carbon atoms having 2 to 12 carbon atoms and R having 0 to 12 carbon atoms;

R is a member of the group consisting of hydrogen and straight and branched chain alkyl radicals having 1 to 12 carbon atoms;

Hyd. Cyc is a saturated radical obtained by saturating a member of the group consisting of cycloalkene and cycloalkadiene radicals having 5 to 10 carbon atoms and dimers, trimers and tetramers thereof;

n is 2, and m, p and q are integers from 1 to 4, l to S,

and 2 to 3, respectively.

2. A composition of matter comprising essentially a mixture of position and geometric isomers of Formula IV of the formulas defined in claim 1.

3. A composition of matter comprising essentially a mixture of position and geometric isomers of Formula V of the formulas. defined in claim 1.

4. A composition of matter comprising essentially a mixture of position and geometric isomers of Formula VI of the formulas, defined in claim 1.

5. A composition of matter comprising essentially a mixture of position and geometric isomers of Formula VII of the formulas. defined in claim 1.

References Cited by the Applicant UNITED STATES PATENTS 2,514,546 7/ 1950 Ipatiefi et al. 260-666 2,526,896 10/1950 Ipatielf et al 260-668 2,622,110 12/1952 IpatiefI et al 260-666 2,623,912 12/1952 Smith 260-668 2,645,669 7/1953 Pines et a1 260-668 2,671,815 3/ 1954 Pines et a1 260-668 2,691,686 10/1954 Bloch 260-671 2,721,226 10/ 1955 Ciapetta et a1 260-667 2,755,317 7/1956 Kassel 260-667 2,765,617 12/1956 Gluesenkamp 208-15 2,842,936 7/ 1958 Ayers et a1 6035.4 2,898,735 8/1959 Carmody ct a1. 6035.4 3,014,081 12/ 1961 Aldridge et a1 260-671 3,105,351 10/ 1963 Stahly 260-667 DELBERT E. GANTZ, Primary Examiner.

LEON D. ROSDOL, ALPHONSO D. SULLIVAN, S. P.

JONES, C. E. SPRESSER, Assistant Examiners. 

1. A COMPOSITION OF MATTER COMPRISING A MIXTURE OF POSITION AND GEOMETRIC ISOMERS OF AT LEAST ONE OF FORMULAS IV, V, VI AND VII, 